JPH04128244A - Modification of alkylnaphthalene mixture - Google Patents
Modification of alkylnaphthalene mixtureInfo
- Publication number
- JPH04128244A JPH04128244A JP2248548A JP24854890A JPH04128244A JP H04128244 A JPH04128244 A JP H04128244A JP 2248548 A JP2248548 A JP 2248548A JP 24854890 A JP24854890 A JP 24854890A JP H04128244 A JPH04128244 A JP H04128244A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- mixture
- catalyst
- hydrogen
- alkylnaphthalene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 230000004048 modification Effects 0.000 title description 3
- 238000012986 modification Methods 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 150000001336 alkenes Chemical class 0.000 claims abstract description 16
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 11
- 239000011973 solid acid Substances 0.000 claims abstract description 11
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 238000002407 reforming Methods 0.000 claims description 4
- 238000007327 hydrogenolysis reaction Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 1
- 239000010457 zeolite Substances 0.000 abstract description 9
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052680 mordenite Inorganic materials 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 229910052697 platinum Inorganic materials 0.000 abstract description 3
- 239000011280 coal tar Substances 0.000 abstract description 2
- 239000000295 fuel oil Substances 0.000 abstract description 2
- 239000003208 petroleum Substances 0.000 abstract description 2
- 239000012808 vapor phase Substances 0.000 abstract 5
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical class C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 17
- YGYNBBAUIYTWBF-UHFFFAOYSA-N 2,6-dimethylnaphthalene Chemical compound C1=C(C)C=CC2=CC(C)=CC=C21 YGYNBBAUIYTWBF-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- UJCIERMQHAXPRF-UHFFFAOYSA-N 2-ethyl-1-methylnaphthalene Chemical compound C1=CC=CC2=C(C)C(CC)=CC=C21 UJCIERMQHAXPRF-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010555 transalkylation reaction Methods 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- -1 aluminum chloride Chemical class 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012013 faujasite Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- XYTKCJHHXQVFCK-UHFFFAOYSA-N 1,3,8-trimethylnaphthalene Chemical compound CC1=CC=CC2=CC(C)=CC(C)=C21 XYTKCJHHXQVFCK-UHFFFAOYSA-N 0.000 description 1
- ZMXIYERNXPIYFR-UHFFFAOYSA-N 1-ethylnaphthalene Chemical compound C1=CC=C2C(CC)=CC=CC2=C1 ZMXIYERNXPIYFR-UHFFFAOYSA-N 0.000 description 1
- IBHYXJLDLKZULZ-UHFFFAOYSA-N 3-ethyl-1,2-dimethylnaphthalene Chemical compound C1=CC=C2C(C)=C(C)C(CC)=CC2=C1 IBHYXJLDLKZULZ-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- RJTJVVYSTUQWNI-UHFFFAOYSA-N beta-ethyl naphthalene Natural products C1=CC=CC2=CC(CC)=CC=C21 RJTJVVYSTUQWNI-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野Ｊ
本発明はアルキルナフタレン混合物の改質方法に関する
ものであり、より詳しくは、アルキルナフタレン混合物
を固体酸触媒及び水素の存在下、変換反応に付してアル
キルナフタレン混合物を改質する方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application J] The present invention relates to a method for reforming an alkylnaphthalene mixture, and more specifically, a method for reforming an alkylnaphthalene mixture in the presence of a solid acid catalyst and hydrogen. The present invention relates to a method for modifying an alkylnaphthalene mixture.
［従来の技術］
アルキルナフタレンのうち、特定の構造を有する化合物
が工業的に多く利用されている。例えば、２，６−シメ
チルナフタレンはガスバリアー性の高いポリエチレンナ
フタレート（ＰＥＮ）等の原料として使用されている。[Prior Art] Among alkylnaphthalenes, compounds having a specific structure are often used industrially. For example, 2,6-dimethylnaphthalene is used as a raw material for polyethylene naphthalate (PEN), which has high gas barrier properties.
しかしながら、アルキルナフタレン混合物に種々の異性
体を有する種々の化合物が含有されている。従って、有
用な特定化合物それ自体の濃度は低いことが多く、その
有効な分離方法が望まれており、また該化合物を分離し
た後に残るその他の成分の有効利用が重要であった。例
えば、２，６−シメチルナフタレンの全ジメチルナフタ
レン異性体中に占める熱力学的平衡濃度は１４％程度で
あり、これを分離した後に残るラフィネートを有効利用
するためには、２，６体の濃度を高めるための変換反応
によるアルキルナフタレンの改質が必要となる。However, alkylnaphthalene mixtures contain different compounds with different isomers. Therefore, the concentration of a useful specific compound itself is often low, and an effective method for separating it is desired, and it is also important to effectively utilize other components remaining after separating the compound. For example, the thermodynamic equilibrium concentration of 2,6-dimethylnaphthalene in all dimethylnaphthalene isomers is about 14%, and in order to effectively utilize the raffinate that remains after separation, it is necessary to It is necessary to modify the alkylnaphthalene by a conversion reaction to increase its concentration.
かかる改質のための変換反応は、異性化、不均化、アル
キル化あるいはトランスアルキル化等の反応が複雑に生
じるものであり、通常、アルミノシリケート、ゼオライ
ト等の種々の固体酸触媒（例えば、Ｋｏｚｏ Ｔａｎａ
ｂｅ ｅｔ ａｌ、 、“Ｎｅｗ ５ｏｌｉｄ Ａｃ１
ｄｓ ａｎｄＢａｓｅｓ” 、 Ｋｏｄａｎｓｈａ −
Ｅｌｓｅｖｉｅｒ、 １９８９等参照）あるいは塩化ア
ルミニウム等の金属ハロゲン化物からなるルイス酸触媒
を用いて水素雰囲気上気相または液相で実施される。特
に、工業的には生成物との分離が容易な固体酸触媒を用
いることが多く、且つ高沸点成分の副生によるコーキン
グを抑制する目的で水素気流下炭化水素蒸気を反応させ
ることが多い。Conversion reactions for such modification involve complex reactions such as isomerization, disproportionation, alkylation, or transalkylation, and are usually carried out using various solid acid catalysts such as aluminosilicates and zeolites (e.g., Kozo Tana
be et al, , “New 5olid Ac1
ds andBases", Kodansha -
Elsevier, 1989, etc.) or a Lewis acid catalyst consisting of a metal halide such as aluminum chloride, and is carried out in a gas or liquid phase in a hydrogen atmosphere. In particular, industrially, solid acid catalysts that are easy to separate from products are often used, and hydrocarbon vapors are often reacted under a hydrogen stream for the purpose of suppressing coking caused by by-products of high-boiling components.
［発明が解決しようとする課題Ｊ
しかしながら、上記の方法で変換反応を行う場合、反応
後の気相の水素中には微量のメタン及びその他エタン、
プロパン等のパラフィン系炭化水素、また、エチレン、
プロピレン等のオレフィン系炭化水素が含まれているこ
とが判明している。[Problem to be Solved by the Invention J] However, when the conversion reaction is carried out by the above method, trace amounts of methane and other ethane,
Paraffinic hydrocarbons such as propane, ethylene,
It has been found that it contains olefinic hydrocarbons such as propylene.
例えば、アルキルナフタレン混合物としてジメチルナフ
タレン混合物を反応原料とした場合、原料中の不純物と
して通常エチルナフタレンが含まれているが、このよう
な不純物からも軽沸炭化水素が生成することが確認され
ており、アルキル基の炭素数が大きくなるほど、いっそ
う炭化水素が生成し易くなる。For example, when a dimethylnaphthalene mixture is used as a reaction raw material as an alkylnaphthalene mixture, ethylnaphthalene is usually included as an impurity in the raw material, but it has been confirmed that light boiling hydrocarbons are also generated from such impurities. As the number of carbon atoms in the alkyl group increases, it becomes easier to generate hydrocarbons.
そして、かかる反応に使用する固体酸触媒等は、アルキ
ルナフタレンを活性化する場合と同様に低級のオレフィ
ンの活性化にも寄与する。従って、反応系から副生ずる
オレフィンとアルキルナフタレンとがアルキル化等の反
応を起こし、より置換度の高いアルキルナフタレンが生
成することとなり、結果として、所望の改質アルキルナ
フタレンを得る際の障害となるという課題がある。The solid acid catalyst used in this reaction also contributes to the activation of lower olefins in the same way as in the case of activating alkylnaphthalenes. Therefore, the olefin by-produced from the reaction system and the alkylnaphthalene undergo reactions such as alkylation, resulting in the production of alkylnaphthalene with a higher degree of substitution, which becomes an obstacle in obtaining the desired modified alkylnaphthalene. There is a problem.
例えば、ジメチルナフタレン異性体混合物を原料として
変換反応に付した場合、上記水素ガスをそのまま循環さ
せるとエチルメチルナフタレン、または、トリアルキル
ナフタレン等のジメチルナフタレン異性体より高沸点の
化合物が生成するようになり、結果として、この場合の
目的化合物である２、６−シメチルナフタレンの収率の
低下を招くこととなる。For example, when a mixture of dimethylnaphthalene isomers is used as a raw material for a conversion reaction, if the hydrogen gas is circulated as is, compounds with higher boiling points than dimethylnaphthalene isomers such as ethylmethylnaphthalene or trialkylnaphthalene will be produced. As a result, the yield of 2,6-dimethylnaphthalene, which is the target compound in this case, decreases.
［課題を解決するための手段Ｊ
そこで、本発明者等は上記の課題を解消すべく鋭意検討
した結果、アルキルナフタレン混合物を出発原料とした
場合に副生ずるオレフィンを除去することにより、優れ
たアルキルナフタレンの改質を行うことができることを
見出し本発明に到達した。[Means for Solving the Problems J] Therefore, as a result of intensive studies in order to solve the above problems, the present inventors have found that an excellent alkyl The inventors discovered that naphthalene can be modified and arrived at the present invention.
すなわち、本発明の目的はアルキルナフタレン混合物を
改質し、特定のアルキルナフタレンを効率よく連続的に
取得する方法を提供するものである。That is, an object of the present invention is to provide a method for efficiently and continuously obtaining a specific alkylnaphthalene by modifying an alkylnaphthalene mixture.
そして、かかる目的は、アルキルナフタレン混合物を固
体酸触媒及び水素存在下、変換反応に付してアルキルナ
フタレン混合物を改質する方法において、変換反応生成
物より改質されたアルキルナフタレン混合物を分離した
後の気相から、前記反応で副生じたオレフィンを除去し
、該気相を水素として前記反応に循環使用することを特
徴とするアルキルナフタレン混合物の改質方法により容
易に達成される。This purpose is achieved in a method of modifying an alkylnaphthalene mixture by subjecting the alkylnaphthalene mixture to a conversion reaction in the presence of a solid acid catalyst and hydrogen, after separating the modified alkylnaphthalene mixture from the conversion reaction product. This can be easily accomplished by a method for reforming an alkylnaphthalene mixture, which is characterized in that the olefin produced as a by-product in the reaction is removed from the gas phase, and the gas phase is recycled to the reaction as hydrogen.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明におけるアルキルナフタレンとは、アルキル基を
ナフタレン環に１個以上有するものであり、モノ体、ジ
体、トリ体、テトラ体等である。アルキル基としては、
好ましくは炭素数１〜５個程度の低級アルキル基、すな
わち、メチル基、エチル基、プロピル基、イソプロピル
基、ブチル基、ペンチル基等である。The alkylnaphthalene in the present invention has one or more alkyl groups in the naphthalene ring, and may be mono, di, tri, tetra, or the like. As an alkyl group,
Preferred are lower alkyl groups having about 1 to 5 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, and pentyl groups.
本発明におけるアルキルナフタレン混合物とは、一般に
石炭タールまた石油系重質油等から得られ通常、アルキ
ルナフタレン成分を５０％以上含む油状物であり、好ま
しくは、蒸留により同じ沸点領域成分を集めた特定のア
ルキルナフタレン混合物である。The alkylnaphthalene mixture in the present invention is an oily substance that is generally obtained from coal tar or petroleum heavy oil, and usually contains 50% or more of an alkylnaphthalene component, and is preferably a specific mixture obtained by collecting components in the same boiling point region by distillation. It is a mixture of alkylnaphthalenes.
特定のアルキルナフタレン混合物として、例えば、ジア
ルキルナフタレン混合物とは、アルキル基の置換位置が
異なる種々の異性体も含むジアルキルナフタレン成分が
、通常５０％以上、好ましくは９０％以上含み、その他
の成分として、通常少量のモノアルキルナフタレン、ナ
フタレン、ビフェニル、インデン、インダン等が含まれ
ている。A specific alkylnaphthalene mixture, for example, a dialkylnaphthalene mixture, usually contains 50% or more, preferably 90% or more, of a dialkylnaphthalene component including various isomers with different substitution positions of the alkyl group, and as other components, It usually contains small amounts of monoalkylnaphthalene, naphthalene, biphenyl, indene, indane, etc.
本発明の変換反応とは、異性化、アルキル化、トランス
アルキル化等の複雑な反応によるものである。アルキル
ナフタレン混合物を原料として変換反応に付した場合、
アルキル基の配置状態が変更改質される。種々の置換基
数を有するアルキルナフタレン混合物を原料とした場合
は、特に置換基数２のジアルキルナフタレンが有利に改
質生成される。The conversion reactions of the present invention are complex reactions such as isomerization, alkylation, and transalkylation. When an alkylnaphthalene mixture is subjected to a conversion reaction as a raw material,
The configuration of the alkyl group is changed and modified. When a mixture of alkylnaphthalenes having various numbers of substituents is used as a raw material, dialkylnaphthalenes having two substituents are particularly advantageously produced by modification.
また、ジアルキルナフタレン混合物を原料とて変換反応
に付した場合は、ジアルキルナフタレンの各異性体の熱
力学的平衡濃度に近い組成の改質混合物が得られる。Further, when a dialkylnaphthalene mixture is used as a raw material and subjected to a conversion reaction, a modified mixture having a composition close to the thermodynamic equilibrium concentration of each isomer of dialkylnaphthalene is obtained.
本発明で使用する固体酸触媒としては、公知の異性化反
応あるいはトランスアルキル化反応等に使用されるもの
であれば特に限定されるものではないが、好ましくはゼ
オライトを主要活性成分とする固体酸触媒がよく、具体
的には、Ｈ−モルデナイト型、Ｈ−ホージャサイト型あ
るいはＨ−ペンタシル型ゼオライト（Ｈ−ＺＳＭ−５型
ヤＨ−ＺＳＭ−１１型等）等が挙げられ、特にＨ−モル
デナイト型、Ｈ−ホージャサイト型あるいはＨ−ＺＳＭ
−５型ゼオライトからなる群から選択された触媒（例え
ば、特開昭５８−２１００３１、ＵＳＰ ４７８３５６
９、ＵＳＰ ４７８３５７０等）を用いるのが好ましい
。なお、これらのＨ型（プロトン）交換ゼオライトのプ
ロトンの一部は金属カチオンでイオン交換されていても
よい。The solid acid catalyst used in the present invention is not particularly limited as long as it is used in known isomerization reactions or transalkylation reactions, but preferably a solid acid catalyst containing zeolite as the main active component. Good catalysts include H-mordenite type, H-faujasite type, and H-pentasil type zeolites (H-ZSM-5 type, H-ZSM-11 type, etc.), and especially H-mordenite type. type, H-faujasite type or H-ZSM
Catalysts selected from the group consisting of Type-5 zeolites (e.g., JP-A-58-210031, USP 478356)
9, USP 4783570, etc.) is preferably used. Note that some of the protons of these H-type (proton) exchanged zeolites may be ion-exchanged with metal cations.
本発明での変換反応は、かかる固体酸触媒の存在下、水
素雰囲気中にアルキルナフタレン混合物を導入して行う
。かかる反応の条件としては、反応温度３００〜５００
°Ｃ１反応圧力は常圧〜３０ ＫＧで水素気流下で行う
のがよく、アルキルナフタレン混合物の供給速度（ＬＨ
８Ｖ）は通常、０．０１〜１０ｈ’、水素の供給量は対
炭化水素モル比で０．１〜１００モルとするのがよい。The conversion reaction in the present invention is carried out by introducing an alkylnaphthalene mixture into a hydrogen atmosphere in the presence of such a solid acid catalyst. Conditions for such a reaction include a reaction temperature of 300 to 500
The reaction pressure at °C1 is from normal pressure to 30 KG, and it is best to carry out under a hydrogen stream, and the feed rate of the alkylnaphthalene mixture (LH
8V) is usually 0.01 to 10 h', and the amount of hydrogen supplied is preferably 0.1 to 100 mol in molar ratio to hydrocarbon.
次に、かかる変換反応生成物より改質されたアルキルナ
フタレン混合物を分離して反応系外に除去する。この場
合の分離方法としては、反応終了後の反応生成物を冷却
することにより容易に行うことができる。Next, the modified alkylnaphthalene mixture is separated from the conversion reaction product and removed from the reaction system. The separation method in this case can be easily carried out by cooling the reaction product after the reaction is completed.
一方、反応に供された水素中には、反応で副生ずる微量
のオレフィンが含まれており、そのまま水素を反応工程
に循環していくとオレフィンが徐々に蓄積し、オレフィ
ンの一部が反応し、変換反応に影響を与える。On the other hand, the hydrogen used in the reaction contains trace amounts of olefins that are produced as by-products in the reaction, and if hydrogen is recycled as is into the reaction process, olefins will gradually accumulate and some of the olefins will react. , affecting the conversion reaction.
そこで、本発明では、かかる循環水素中に含有蓄積され
ていくオレフィン性化合物を除去する。Therefore, in the present invention, the olefinic compounds that are accumulated in the circulating hydrogen are removed.
除去する方法としては、オレフィンの水素化、水素分解
、重合、吸着、抽出等特に限定されないが、低級オレフ
ィンに対して水素化触媒およびｌまたは水素化分解能を
有する触媒存在下で反応させて除去する方法が好ましい
。Methods for removing olefins include hydrogenation, hydrogen cracking, polymerization, adsorption, and extraction of olefins, but are not particularly limited. Lower olefins are removed by reacting them in the presence of a hydrogenation catalyst and a catalyst capable of hydrogenation cracking. The method is preferred.
このような触媒としては、ニッケル、コバルト、パラジ
ウム、ルテニウム、白金、イリジウムあるいはロジウム
等の金属触媒やこれらの金属を担体に担持した担持触媒
が挙げられる。好ましくは、担持ニッケル、担持ルテニ
ウム、担持白金等の触媒を用いるのがよい。担体として
はアルミナが一般的に使用されるが、特にこれに限定さ
れるものではない。Examples of such catalysts include metal catalysts such as nickel, cobalt, palladium, ruthenium, platinum, iridium, and rhodium, and supported catalysts in which these metals are supported on a carrier. Preferably, a catalyst such as supported nickel, supported ruthenium, or supported platinum is used. Alumina is generally used as the carrier, but is not particularly limited thereto.
担持触媒を使用する場合、金属担持量は通常０．１〜５
０％であり、この反応の条件としては、反応温度が通常
１００〜５００°Ｃ１好ましくは２５０〜４００°Ｃ１
反応圧力が通常、常圧〜１００ ＫＧである。また、上
記の気体反応生成物の供給速度（ＧＨ８Ｖ ）としては
、通常１００〜１０００００ｈ・１、好ましくは２００
０〜２００００ｈ−１である。When using a supported catalyst, the amount of metal supported is usually 0.1 to 5
0%, and the conditions for this reaction are that the reaction temperature is usually 100 to 500°C, preferably 250 to 400°C.
The reaction pressure is usually normal pressure to 100 KG. Further, the supply rate (GH8V) of the above gaseous reaction product is usually 100 to 100,000 h·1, preferably 200
It is 0 to 20000h-1.
その他の方法として、ゼオライト、活性炭、アルミナ、
シリカゲル等の吸着剤を用いた吸着分離法、また、水素
分子を選択的透過する性質を用いたパラジウム合金膜法
等が利用できる。Other methods include zeolite, activated carbon, alumina,
An adsorption separation method using an adsorbent such as silica gel, a palladium alloy membrane method using a property of selectively permeating hydrogen molecules, etc. can be used.
本発明では、かかる処理により気体状反応生成物中に含
有されるオレフィンが低級パラフィンに変換されること
などによりオレフィン性化合物が除去される。そして、
オレフィンが除去され低級パラフィンを含有する水素を
前述の変換反応帯域に循環して再使用する。In the present invention, olefinic compounds are removed by converting the olefins contained in the gaseous reaction product into lower paraffins through such treatment. and,
The olefin-removed hydrogen containing lower paraffins is recycled to the aforementioned conversion reaction zone for reuse.
［実施例］
以下、本発明を実施例により具体的に説明するが、本発
明はその要旨を越えない限り下記の実施例に限定される
ものではない。[Examples] Hereinafter, the present invention will be specifically explained using Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.
なお、原料、反応物についてはガスクロマトグラフィー
及びガスクロマトグラフィー質量分析計により分析を行
った。The raw materials and reactants were analyzed using gas chromatography and gas chromatography mass spectrometry.
参考例１
クロマト分離により、２，６−ジメチルナフタレンの濃
度の低下したジメチルナフタレン混合物（２，６−シメ
チルナフタレン０．９％、その他のジメチルナフタレン
混合物体８９．６％、その他少量のモノア、ルキルナフ
タレン、ビフェニル等を含む）を用いて変換反応を行っ
た。Reference Example 1 A dimethylnaphthalene mixture with a reduced concentration of 2,6-dimethylnaphthalene due to chromatographic separation (2,6-dimethylnaphthalene 0.9%, other dimethylnaphthalene mixtures 89.6%, other small amounts of monomer, Conversion reactions were carried out using a variety of compounds (including alkylnaphthalene, biphenyl, etc.).
触媒としてＺＳＭ −５型ゼオライト（ＳｉＯ２／Ａｌ
２０３＝３２．５ ）を焼成し、次いでＮＨＡ＋型へイ
オン交換し、更に焼成してＨ÷型に変換して得られたＨ
−ＺＳＭ−５型ゼオライトを打錠成型したものを使用し
た。ZSM-5 type zeolite (SiO2/Al
H
-ZSM-5 type zeolite was used.
内径２０ｍｍの硬質ガラス製反応器に、上記の触媒（粒
径１０〜２０メツシーＬ ） ３．１ｇ （５，２ｍｌ
）を充填し、触媒層の上にはガラスピーズ層を充填し
、これに上記のジメチルナフタレン混合物（ＤＭＮ）を
純粋な水素ガス中に気化同伴させて供給し、温度３９０
°Ｃ１圧力１０ｋｇ ／ ｃｍ２、Ｈ２／ＤＭＮ（モル
比）＝２５、ＬＨ８Ｖ ＝ ０．６で流通して変換反応
を行なった。In a hard glass reactor with an inner diameter of 20 mm, 3.1 g (5.2 ml
), a layer of glass beads was filled on top of the catalyst layer, and the above dimethylnaphthalene mixture (DMN) was vaporized and entrained in pure hydrogen gas and supplied thereto, at a temperature of 390°C.
The conversion reaction was carried out by flowing at °C1 pressure of 10 kg/cm2, H2/DMN (molar ratio) = 25, and LH8V = 0.6.
反応生成液中の、２，６−ジメチルナフタレンの全ジメ
チルナフタレンに占める濃度は１３．２％に向上した。The concentration of 2,6-dimethylnaphthalene in the total dimethylnaphthalene in the reaction product liquid increased to 13.2%.
またエチルメチルナフタレンは検出されなかった。Furthermore, ethylmethylnaphthalene was not detected.
一方、反応生成液分離後の気相中の生成ガスは０．４％
（水素９９．６％）であり、その組織は以下の通りであ
る。On the other hand, the product gas in the gas phase after separation of the reaction product liquid is 0.4%
(99.6% hydrogen), and its structure is as follows.
参考例２
純粋な水素の代わりにエチレン２．５％を含有する水素
ガスを使用した以外は参考例１と同様に反応を行った。Reference Example 2 A reaction was carried out in the same manner as in Reference Example 1, except that hydrogen gas containing 2.5% ethylene was used instead of pure hydrogen.
その結果、ジメチルナフタレン異性体混合物中の２，６
−ジメチルナフタレン濃度に関しては１３．０％であっ
たが、微量のベンゼン、トルエン、キシレン、エチルベ
ンゼン等の軽沸成分、エチルメチルナフタレン、エチル
ジメチルナフタレン、トリメチルナフタレン等の高沸成
分の生成が確認された。As a result, 2,6 in the dimethylnaphthalene isomer mixture
-The concentration of dimethylnaphthalene was 13.0%, but trace amounts of light boiling components such as benzene, toluene, xylene, and ethylbenzene, and high boiling components such as ethylmethylnaphthalene, ethyldimethylnaphthalene, and trimethylnaphthalene were confirmed to be produced. Ta.
参考例３
純粋な水素の代わりにメタン２．５％を含有する水素ガ
スを使用した以外は参考例１と同様に反応を行ったが、
反応への影響は認められながった。Reference Example 3 The reaction was carried out in the same manner as Reference Example 1, except that hydrogen gas containing 2.5% methane was used instead of pure hydrogen.
No effect on reaction was observed.
実施例
参考例１で生成したガスを含む水素ガスを水素化分解触
媒に導き、無害化した。触媒はアルミナ担持ルテニウム
触媒（担持率０．５％）を用い、３６０’Ｃ１１０ｋｇ
／ｃｍ’、水素供給速度１００００ｈ４で反応を行った
ところ、生成ガス中のオレフィン分は消失し、また全炭
化水素中のメタンの割合は４５％に達し、少なくとも低
級炭化水素の一部はメタン化しているのが明らかになっ
た。かかる低級炭化水素を含有した水素ガスを用いて参
考例１と同様に変換反応を行ったところ、反応への影響
は認められなかった。The hydrogen gas containing the gas produced in Example Reference Example 1 was introduced into a hydrogenolysis catalyst and rendered harmless. The catalyst used was an alumina-supported ruthenium catalyst (support rate 0.5%), 360'C110kg.
/cm', when the reaction was carried out at a hydrogen supply rate of 10,000h4, the olefin content in the produced gas disappeared, and the proportion of methane in the total hydrocarbons reached 45%, and at least a part of the lower hydrocarbons was methanated. It became clear that When a conversion reaction was carried out in the same manner as in Reference Example 1 using hydrogen gas containing such lower hydrocarbons, no influence on the reaction was observed.
比較例
参考例１の反応生成ガスを含む水素を純粋な水素の代わ
りに直接そのまま用いた以外は、参考例１と同様に反応
を行ったところ、反応生成液中の２．６−ジメチルナフ
タレンの全ジメチルナフタレ異性体に占める濃度は１３
．０％であり、また、エチルメチルナフタレンがわずか
に検出された。一方、反応生成ガスの組成は実施例１と
ほぼ同様であったが、生成ガスの量は水素全体に対し０
．７％に増加した。Comparative Example The reaction was carried out in the same manner as in Reference Example 1, except that the hydrogen containing the reaction product gas in Reference Example 1 was directly used instead of pure hydrogen. The concentration of all dimethylnaphthalene isomers is 13
．． 0%, and a small amount of ethylmethylnaphthalene was detected. On the other hand, the composition of the reaction product gas was almost the same as in Example 1, but the amount of product gas was 0% relative to the total hydrogen.
．． It increased to 7%.
［発明の効果］
本発明によれば、反応系内にオレフィン性化合物の蓄積
を生じることなく、所望のジアルキルナフタレンを効率
よく得ることができ、
本物質の工
業的生産に寄与するところが太きい。[Effects of the Invention] According to the present invention, the desired dialkylnaphthalene can be efficiently obtained without causing the accumulation of olefinic compounds in the reaction system, which greatly contributes to the industrial production of the present substance.
Claims (4)
素の存在下変換反応に付してアルキルナフタレン混合物
を改質する方法において、変換反応生成物より改質され
たアルキルナフタレン混合物を分離した後の気相から、
前記反応で副生したオレフィンを除去し、該気相を水素
として前記反応に循環使用することを特徴するアルキル
ナフタレン混合物の改質方法。(1) In a method of modifying an alkylnaphthalene mixture by subjecting the alkylnaphthalene mixture to a conversion reaction in the presence of a solid acid catalyst and hydrogen, the gas phase after separating the modified alkylnaphthalene mixture from the conversion reaction product. from,
A method for reforming an alkylnaphthalene mixture, comprising removing the olefin by-produced in the reaction and recycling the gas phase as hydrogen in the reaction.
有する触媒と接触させてオレフィンを除去することを特
徴とする請求項１記載の方法。(2) The method according to claim 1, characterized in that the olefin is removed by bringing the gas phase into contact with a hydrogenation catalyst and/or a catalyst having hydrogenolysis ability.
キルナフタレンを含むことを特徴とする請求項１記載の
方法。3. The method of claim 1, wherein the alkylnaphthalene mixture contains 50% or more dialkylnaphthalene.
項１記載の方法。(4) The method according to claim 1, characterized in that the conversion reaction is carried out in the gas phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2248548A JP2817382B2 (en) | 1990-09-18 | 1990-09-18 | Method for modifying alkyl naphthalene mixture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2248548A JP2817382B2 (en) | 1990-09-18 | 1990-09-18 | Method for modifying alkyl naphthalene mixture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04128244A true JPH04128244A (en) | 1992-04-28 |
| JP2817382B2 JP2817382B2 (en) | 1998-10-30 |
Family
ID=17179817
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2248548A Expired - Fee Related JP2817382B2 (en) | 1990-09-18 | 1990-09-18 | Method for modifying alkyl naphthalene mixture |
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109777575A (en) * | 2019-02-16 | 2019-05-21 | 龙蟠润滑新材料（天津）有限公司 | A kind of wind power generating set gear oil and preparation method thereof |
-
1990
- 1990-09-18 JP JP2248548A patent/JP2817382B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109777575A (en) * | 2019-02-16 | 2019-05-21 | 龙蟠润滑新材料（天津）有限公司 | A kind of wind power generating set gear oil and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2817382B2 (en) | 1998-10-30 |
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